Synthesis Of Chabazite-Containing Molecular Sieves And Their Use In The Conversion Of Oxygenates To Olefins

ABSTRACT

In a method of synthesizing a mostly CHA-type silicoaluminophosphate sieve, a reaction mixture comprises sources of water, silicon, aluminum, phosphorus, and a template. In one aspect, when the reaction mixture Si/Al 2  ratio is less than 0.33, crystallization is induced at least 165° C. Advantageously, the sieve so crystallized exhibits a Si/Al 2  ratio less than 0.33 and/or at least 0.10 greater than the synthesis mixture Si/Al 2  ratio. In another aspect, the aluminum and phosphorus sources are first combined to form a primary mixture that is aged. The silicon source and template can then be added to form the synthesis mixture. After inducing crystallization, in this aspect, both the synthesis mixture and crystallized sieve exhibit a Si/Al 2  ratio less than 0.33 and/or the crystallized sieve has an average crystal size not more than 3.0 μm. The molecular sieve from both aspects can be used in a hydrocarbon (oxygenates-to-olefins) conversion process.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is related to, and claims priority to, U.S. Ser.No. 61/083,760, U.S. Ser. No. 61/083,765, U.S. Ser. No. 61/083,775, andU.S. Ser. No. 61/083,749, each filed on Jul. 25, 2008 and entitled,“Synthesis of Chabazite-Containing Molecular Sieves and Their Use in theConversion of Oxygenates to Olefins,” the entire disclosures of each ofwhich are hereby incorporated by reference herein.

FIELD OF THE INVENTION

This invention relates to the synthesis of chabazite-type containingmolecular sieves and their use in the conversion of oxygenates,particularly methanol, to olefins, particularly ethylene and/orpropylene.

BACKGROUND OF THE INVENTION

The conversion of oxygenates to olefins (OTO) is currently the subjectof intense research because it has the potential for replacing thelong-standing steam cracking technology that is today theindustry-standard for producing world scale quantities of ethylene andpropylene. The very large volumes involved suggest that substantialeconomic incentives exist for alternate technologies that can deliverhigh throughputs of light olefins in a cost efficient manner. Whereassteam cracking relies on non-selective thermal reactions of naphtharange hydrocarbons at very high temperatures, OTO exploits catalytic andmicro-architectural properties of acidic molecular sieves under mildertemperature conditions to produce high yields of ethylene and propylenefrom methanol.

Current understanding of the OTO reactions suggests a complex sequencein which three major steps can be identified: (1) an induction periodleading to the formation of an active carbon pool (alkyl-aromatics), (2)alkylation-dealkylation reactions of these active intermediates leadingto products, and (3) a gradual build-up of condensed ring aromatics. OTOis therefore an inherently transient chemical transformation in whichthe catalyst is in a continuous state of change. The ability of thecatalyst to maintain high olefin yields for prolonged periods of timerelies on a delicate balance between the relative rates at which theabove processes take place. The formation of coke-like molecules is ofsingular importance because their accumulation interferes with thedesired reaction sequence in a number of ways. In particular, cokerenders the carbon pool inactive, lowers the rates of diffusion ofreactants and products, increases the potential for undesired secondaryreactions and limits catalyst life.

Over the last two decades, many catalytic materials have been identifiedas being useful for carrying out the OTO reactions. Crystallinemolecular sieves are the preferred catalysts today because theysimultaneously address the acidity and morphological requirements forthe reactions. Particularly preferred materials are eight-membered ringaluminosilicates, such as those having the chabazite (CHA) frameworktype, as well as aluminophosphates (AlPOs) and silicoaluminophosphates(SAPOs) of the CHA framework type, such as SAPO-34.

Chabazite is a naturally occurring zeolite with the approximate formulaCa₆Al₁₂Si₂₄O₇₂. Three synthetic forms of chabazite are described in“Zeolite Molecular Sieves”, by D. W. Breck, published in 1973 by JohnWiley & Sons, the complete disclosure of which is incorporated herein byspecific reference. The three synthetic forms reported by Breck areZeolite “K-G”, described in J. Chem. Soc., p. 2822 (1956), Barrer et al;Zeolite D, described in British Patent No. 868,846 (1961); and ZeoliteR, described in U.S. Pat. No. 3,030,181 (1962). Zeolite K-G zeolite hasa silica:alumina mole ratio of 2.3:1 to 4.15:1, whereas zeolites D and Rhave silica:alumina mole ratios of 4.5:1 to 4.9:1 and 3.45:1 to 3.65:1,respectively.

In U.S. Pat. No. 4,440,871, the synthesis of a wide variety of SAPOmaterials of various framework types is described with a number ofspecific examples. Also disclosed are a large number of possible organictemplates, with some specific examples. In the specific examples anumber of CHA framework type materials are described. The preparation ofSAPO-34 is reported, using tetraethylammonium hydroxide (TEAOH), orisopropylamine, or mixtures of TEAOH and dipropylamine (DPA) astemplates. Also disclosed is a specific example that utilizescyclohexylamine in the preparation of SAPO-44. Although other templatematerials are described, there are no other templates indicated as beingsuitable for preparing SAPO's of the CHA framework type.

U.S. Pat. No. 6,162,415 discloses the synthesis of asilicoaluminophosphate molecular sieve, SAPO-44, which has a CHAframework type in the presence of a directing agent comprisingcyclohexylamine or a cyclohexylammonium salt, such as cyclohexylammoniumchloride or cyclohexylammonium bromide.

Silicoaluminophosphates of the CHA framework type with low siliconcontents are particularly desirable for use in the methanol-to-olefinsprocess. Thus, Wilson, et al., Microporous and Mesoporous Materials, 29,117-126, 1999 report that it is beneficial to have lower Si content formethanol-to-olefins reaction, in particular because low Si content hasthe effect of reducing propane formation and decreasing catalystdeactivation.

U.S. Pat. No. 6,620,983 discloses a method for preparingsilicoaluminophosphate molecular sieves, and in particular low silicasilicoaluminophosphate molecular sieve having a Si/Al atomic ratio ofless than 0.5, which process comprises forming a reaction mixturecomprising a source of aluminum, a source of silicon, a source ofphosphorus, at least one organic template, at least one compound whichcomprises two or more fluorine substituents and capable of providingfluoride ions, and inducing crystallization of thesilicoaluminophosphate molecular sieve from the reaction mixture.Suitable organic templates are said to include one or more of tetraethylammonium hydroxide, tetraethyl ammonium phosphate, tetraethyl ammoniumfluoride, tetraethyl ammonium bromide, tetraethyl ammonium chloride,tetraethyl ammonium acetate, dipropylamine, isopropylamine,cyclohexylamine, morpholine, methylbutylamine, morpholine,diethanolamine, and triethylamine. In the Examples, crystallization isconducted by heating the reaction mixture to 170° C. over 18 hours andthen holding the mixture at this temperature for 18 hours to 4 days.

U.S. Pat. No. 6,793,901 discloses a method for preparing a microporoussilicoaluminophosphate molecular sieve having the CHA framework type,which process comprises (a) forming a reaction mixture comprising asource of aluminum, a source of silicon, a source of phosphorus,optionally at least one source of fluoride ions and at least onetemplate containing one or more N,N-dimethylamino moieties, (b) inducingcrystallization of the silicoaluminophosphate molecular sieve from thereaction mixture, and (c) recovering silicoaluminophosphate molecularsieve from the reaction mixture. Suitable templates are said to includeone or more of N,N-dimethylethanolamine, N,N-dimethylbutanolamine,N,N-dimethylheptanolamine, N,N-dimethylhexanolamine,N,N-dimethylethylenediamine, N,N-dimethylpropylenediamine,N,N-dimethylbutylene-diamine, N,N-dimethylheptylenediamine,N,N-dimethylhexylenediamine, or dimethyl-ethylamine,dimethylpropylamine, dimethyl-heptylamine, and dimethylhexylamine. Whenconducted in the presence of fluoride ions, the synthesis is effectivein producing low silica silicoaluminophosphate molecular sieves having aSi/Al atomic ratio of from 0.01 to 0.1. In the Examples, crystallizationis conducted by heating the reaction mixture to 170 to 180° C. for 1 to5 days.

U.S. Pat. No. 6,835,363 discloses a process for preparing microporouscrystalline silicoaluminophosphate molecular sieves of CHA frameworktype, the process comprising: (a) providing a reaction mixturecomprising a source of alumina, a source of phosphate, a source ofsilica, hydrogen fluoride and an organic template comprising one or morecompounds of formula (I):

(CH₃)₂N—R—N(CH₃)₂

where R is an alkyl radical of from 1 to 12 carbon atoms; (b) inducingcrystallization of silicoaluminophosphate from the reaction mixture; and(c) recovering silicoaluminophosphate molecular sieve. Suitabletemplates are said to include one or more of the group consisting of:N,N,N′,N′-tetramethyl-1,3-propane-diamine,N,N,N′,N′-tetramethyl-1,4-butanediamine,N,N,N′,N′-tetramethyl-1,3-butanediamine,N,N,N′,N′-tetramethyl-1,5-pentanediamine,N,N,N′,N′-tetramethyl-1,6-hexanediamine,N,N,N′,N′-tetramethyl-1,7-heptanediamine,N,N,N′,N′-tetramethyl-1,8-octanediamine,N,N,N′,N′-tetramethyl-1,9-nonanediamineN,N,N′,N′-tetramethyl-1,10-decanediamine,N,N,N′,N′-tetramethyl-1,11-undecanediamine andN,N,N′,N′-tetramethyl-1,12-dodecanediamine. In the Examples,crystallization is conducted by heating the reaction mixture to 120 to200° C. for 4 to 48 hours.

U.S. Pat. No. 7,247,287 discloses the synthesis ofsilicoaluminophosphate molecular sieves having the CHA framework typeemploying a directing agent having the formula:

R¹R²N—R³

wherein R¹ and R² are independently selected from the group consistingof alkyl groups having from 1 to 3 carbon atoms and hydroxyalkyl groupshaving from 1 to 3 carbon atoms and R³ is selected from the groupconsisting of 4- to 8-membered cycloalkyl groups, optionally substitutedby 1 to 3 alkyl groups having from 1 to 3 carbon atoms; and 4- to8-membered heterocyclic groups having from 1 to 3 heteroatoms, saidheterocyclic groups being optionally substituted by 1 to 3 alkyl groupshaving from 1 to 3 carbon atoms and the heteroatoms in said heterocyclicgroups being selected from the group consisting of O, N, and S.Preferably, the directing agent is selected fromN,N-dimethylcyclohexylamine, N,N-dimethyl-methylcyclohexylamine,N,N-dimethyl-cyclopentylamine, N,N-dimethyl-methyl-cyclopentylamine,N,N-dimethylcycloheptyl-amine, N,N-dimethyl-methylcycloheptylamine, andmost preferably is N,N-dimethyl-cyclohexylamine. The synthesis can beeffected with or without the presence of fluoride ions and, in theExamples, crystallization is conducted by heating the reaction mixtureto 180° C. for 3 to 7 days.

When any molecular sieve is used as an oxygenate conversion catalyst,three of the main economic drivers in evaluating the efficiency andprecision of the manufacturing process are the yield of the molecularsieve catalyst, the template efficiency, and the accuracy to which theacid site density of the molecular sieve product can be controlled fromthe component ingredients. In practice, even small changes in yield,template efficiency, and/or acid site density can have an enormouseffect on the economics of a commercial process, and hence there is acontinuing need to develop catalysts with improved yields, improvedtemplate efficiencies, and/or improved accuracy of acid site densitiesfor use in oxygenate conversion.

The Si/Al₂ molar ratio is one key parameter to control the acid sitedensity and therefore the catalytic activity. This is easily done athigher Si/Al₂ ratios, where the Si/Al₂ ratio of the product compositionis adjustable by changing the Si/Al₂ ratio of the synthesis mixture. Inorder to obtain molecular sieve catalysts with a low bulk Si/A₂ molarratio (e.g., no more than about 0.15, preferably no more than about0.10), it has typically not been sufficient merely to reduce the Si/Al₂ratio of the components of the synthesis mixture. In previous cases,this has only led to formation of molecular sieve products exhibiting arelatively high Si/Al₂ but which are recovered in relatively low yield.According to a first aspect of the invention, it has been discoveredthat a crystallization temperature of at least 165° C. can unexpectedlyallow formation of molecular sieve materials with more controlled Si/Al₂ratios (and thus more controlled acid site densities, i.e., with Si/Al₂ratios and/or acid site densities in the recovered product that arecloser to the relatively low Si/Al₂ ratios in the synthesis mixture).

According to a second aspect of the invention, it has unexpectedly beenfound that the mixing procedure, or more accurately the order ofaddition and relative homogenization of the synthesis mixturecomponents, in silicoaluminophosphate molecular sieve formulations canenhance certain desirable properties, such as reducing the crystal sizeof the product, while still maintaining an acceptable product yield.Surprisingly, the procedure of mixing the sources of aluminum andphosphorus first, and allowing this mixture to age to facilitate moreintimate combination, prior to the addition of the source of silicon, isa robust way to make the synthesis mixture and can result in moredesirable molecular sieve products.

SUMMARY OF THE INVENTION

In a first aspect, the invention relates to a method of preparing asilicoaluminophosphate molecular sieve having a controlled acid sitedensity, the method comprising: (a) providing a synthesis mixturecomprising a source of aluminum, a source of phosphorus, a source ofsilicon, and at least one organic template containing (i) a 4- to8-membered cycloalkyl group, optionally substituted by 1-3 alkyl groupshaving from 1-3 carbon atoms, or (ii) a 4- to 8-membered heterocyclicgroup having from 1-3 heteroatoms, said heterocyclic group beingoptionally substituted by 1-3 alkyl groups having from 1-3 carbon atoms,and said heteroatoms in said heterocyclic groups being selected from thegroup consisting of O, N, and S, wherein the synthesis mixture exhibitsa Si/Al₂ ratio less than 0.33; and (b) inducing crystallization of asilicoaluminophosphate molecular sieve, which exhibits 90% or greaterCHA framework type character, from said synthesis mixture at acrystallization temperature of at least 165° C. for a crystallizationtime from about 5 minutes to about 350 hours to form a crystallizedsilicoaluminophosphate molecular sieve having a crystal sizedistribution such that its average crystal size is not greater than 3.0μm, wherein (i) the crystallized silicoaluminophosphate molecular sieveexhibits a Si/Al₂ ratio less than 0.33, (ii) the crystallizedsilicoaluminophosphate molecular sieve exhibits a Si/Al₂ ratio not morethan 0.10 greater than the Si/Al₂ ratio of the synthesis mixture, or(iii) both (i) and (ii).

In a second aspect, the invention relates to a method of preparing asilicoaluminophosphate molecular sieve having a desired crystal size,the method comprising: (a) combining a source of phosphorus and a sourceof aluminum, optionally with a liquid mixture medium, to form a primarymixture; (b) aging the primary mixture for an aging time and under agingconditions sufficient to allow homogenization of the primary mixture,physico-chemical interaction between the source of phosphorus and thesource of aluminum, or both; (c) adding a source of silicon, at leastone organic template, and optionally additional liquid mixture medium,to the aged primary mixture to form a synthesis mixture; and (d)inducing crystallization of a silicoaluminophosphate molecular sieve,which exhibits 90% or greater CHA framework type character, from saidsynthesis mixture at a crystallization temperature, wherein the at leastone organic template contains (i) a 4- to 8-membered cycloalkyl group,optionally substituted by 1-3 alkyl groups having from 1-3 carbon atoms,or (ii) a 4- to 8-membered heterocyclic group having from 1-3heteroatoms, said heterocyclic group being optionally substituted by 1-3alkyl groups having from 1-3 carbon atoms, and said heteroatoms in saidheterocyclic groups being selected from the group consisting of O, N,and S, wherein the synthesis mixture and the crystallizedsilicoaluminophosphate molecular sieve both exhibit a Si/Al₂ ratio lessthan 0.33, and wherein the crystallized silicoaluminophosphate molecularsieve has a crystal size distribution such that its average crystal sizeis not greater than 3.0 μm.

In another aspect, the invention relates to a method of convertinghydrocarbons into olefins comprising: (a) preparing asilicoaluminophosphate molecular sieve according to the method of thefirst two aspects of the invention; (b) formulating saidsilicoaluminophosphate molecular sieve, along with a binder andoptionally a matrix material, into a silicoaluminophosphate molecularsieve catalyst composition comprising from at least 10% to about 50%molecular sieve; and (c) contacting said catalyst composition with ahydrocarbon feed under conditions sufficient to convert said hydrocarbonfeed into a product comprising predominantly one or more olefins.

In another aspect, the invention relates to a method of forming anolefin-based polymer product comprising: (a) preparing asilicoaluminophosphate molecular sieve according to the method of thefirst two aspects of the invention; (b) formulating saidsilicoaluminophosphate molecular sieve, along with a binder andoptionally a matrix material, into a silicoaluminophosphate molecularsieve catalyst composition comprising from at least 10% to about 50%molecular sieve; (c) contacting said catalyst composition with ahydrocarbon feed under conditions sufficient to convert said hydrocarbonfeed into a product comprising predominantly one or more olefins; and(d) polymerizing at least one of the one or more olefins, optionallywith one or more other comonomers and optionally in the presence of apolymerization catalyst, under conditions sufficient to form anolefin-based (co)polymer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a graph comparing the Si/Al₂ ratios of the variousmolecular sieves of Examples 1-8 and Comparative Examples A-H.

FIG. 2 shows a graph comparing the yields of the various molecularsieves of Examples 1-8 and Comparative Examples A-H.

FIG. 3 shows an SEM micrograph of a sample made according to the methodin Comparative Example I.

FIG. 4 shows an SEM micrograph of a sample made according to the methodin Comparative Example J.

FIG. 5 shows an SEM micrograph of a sample made according to the methodin Example 9.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Described herein is a method of synthesizing a crystallinealuminophosphate or silicoaluminophosphate containing a molecular sievehaving 90% or greater CHA framework-type character and to the use of theresultant molecular sieve as a catalyst in organic conversion reactions,especially the conversion of oxygenates to light olefins.

In a first aspect of the invention in particular, it has been foundthat, by crystallizing at a crystallization temperature of at least 165°C. in the molecular sieve synthesis, it is possible to produce a CHAframework-type containing molecular sieve having a crystal sizedistribution such that its average crystal size is not greater than 3.0μm, having a relatively low Si/Al₂ ratio (e.g., not more than about0.10) in the product, and/or having an increased accuracy (i.e.,decreased difference) between the Si/Al₂ ratio in the initial mixtureand the Si/Al₂ ratio in the product.

In a second aspect of the invention in particular, it has been foundthat, by employing a particular order of addition of components (i.e.,phosphorus and aluminum sources being combined first) in the molecularsieve synthesis, it is possible to produce a CHA framework-typecontaining molecular sieve (particularly having a relatively low Si/Al₂ratio, e.g. not more than about 0.10, in the product and/or in themixture) having a desirably reduced crystal size, e.g., no greater than3.0 microns instead of over 4 microns.

In the present method, a reaction mixture is prepared comprising asource of aluminum, a source of phosphorous, at least one organicdirecting agent, and, optionally, a source of silicon. Any organicdirecting agent capable of directing the synthesis of CHA framework typemolecular sieves can be employed, but generally the directing agent is acompound having the formula (I):

R¹R²N—R³  (I)

wherein R¹ and R² are independently selected from the group consistingof alkyl groups having from 1 to 3 carbon atoms and hydroxyalkyl groupshaving from 1 to 3 carbon atoms and R³ is selected from the groupconsisting of 4- to 8-membered cycloalkyl groups, optionally substitutedby 1 to 3 alkyl groups having from 1 to 3 carbon atoms; and 4- to8-membered heterocyclic groups having from 1 to 3 heteroatoms, saidheterocyclic groups being optionally substituted by 1 to 3 alkyl groupshaving from 1 to 3 carbon atoms and the heteroatoms in said heterocyclicgroups being selected from the group consisting of O, N, and S.

More particularly, the organic directing agent is a compound having theformula (II):

(CH₃)₂N—R³  (II)

wherein R³ is a 4- to 8-membered cycloalkyl group, especially acyclohexyl group, optionally substituted by 1 to 3 methyl groups.Particular examples of suitable organic directing agents include, butare not limited to, at least one of N,N-dimethyl-cyclohexylamine,N,N-dimethyl-methylcyclohexylamine, N,N-dimethyl-cyclopentylamine,N,N-dimethyl-methylcycl-opentylamine, N,N-dimethyl-cycloheptylamine, andN,N-dimethyl-methylcycloheptylamine, especiallyN,N-dimethyl-cyclohexylamine.

The sources of aluminum, phosphorus, and silicon suitable for use in thepresent synthesis method are typically those known in the art or asdescribed in the literature for the production of aluminophosphates andsilicoaluminophosphates. For example, the aluminum source may be analuminum oxide (alumina), optionally hydrated, an aluminum salt,especially a phosphate, an aluminate, or a mixture thereof. Othersources may include alumina sols or organic alumina sources, e.g.,aluminum alkoxides such as aluminum isopropoxide. A preferred source isa hydrated alumina, most preferably pseudoboehmite, which contains about75% Al₂O₃ and 25% H₂O by weight. Typically, the source of phosphorus isa phosphoric acid, especially orthophosphoric acid, although otherphosphorus sources, for example, organophosphates (e.g.trialkylphosphates such as triethylphosphate) and aluminophosphates maybe used. When organophosphates and/or aluminophosphates are used,typically they are present collectively in a minor amount (i.e., lessthan 50% by weight of the phosphorus source) in combination with amajority (i.e., at least 50% by weight of the phosphorus source) of aninorganic phosphorus source (such as phosphoric acid). Suitable sourcesof silicon include silica, for example colloidal silica and fumedsilica, as well as organic silicon source, e.g. a tetraalkylorthosilicate such as tetraethylorthosilicate (TEOS),tetramethylorthosilicate (TMOS), or the like, or a combination thereof.

Although, in most embodiments, the sources of silicon, phosphorus, andaluminum are the only components that form the framework of a calcinedsilicoaluminophosphate molecular sieve according to the invention, it ispossible for some small portion (e.g., typically no more than about 10wt %, preferably no more than about 5 wt %) of the silicon source can besubstituted with a source of one or more of magnesium, zinc, iron,cobalt, nickel, manganese, and chromium.

In some embodiments, the reaction mixture can have a molar compositionwithin the following ranges:

-   -   P₂O₅: Al₂O₃ from about 0.75 to about 1.25,    -   SiO₂: Al₂O₃ from about 0.01 to about 0.32,    -   H₂O: Al₂O₃ from about 25 to about 50, and    -   SDA: Al₂O₃ from about 1 to about 3,        where SDA designates the structure directing agent (template),        and wherein the molar ratios for the aluminum, phosphorus, and        silicon sources are calculated based on the oxide forms,        regardless of the form of the source added to the reaction        mixture (e.g., whether the phosphorus source is added to the        reaction mixture as phosphoric acid, H₃PO₄, or as        triethylphosphate, the molar ratio is normalized to P₂O₅ molar        equivalents).

Although the reaction mixture may also contain a source of fluorideions, it is found that the present synthesis will proceed in the absenceof fluoride ions, and hence it is generally preferred to employ areaction mixture which is substantially free of fluoride ions.

Typically, the reaction mixture also contains seeds to facilitate thecrystallization process. The amount of seeds employed can vary widely,but generally the reaction mixture comprises from about 0.01 ppm byweight to about 10,000 ppm by weight, such as from about 100 ppm byweight to about 5,000 by weight, of said seeds. Generally, the seeds canbe homostructural with the desired product, that is are of a CHAframework type material, although heterostructural seeds of, forexample, an AEI, LEV, ERI, AFX, or OFF framework-type molecular sieve,or a combination or intergrowth thereof, may be used. The seeds may beadded to the reaction mixture as a suspension in a liquid medium, suchas water; in some cases, particularly where the seeds are of relativelysmall size, the suspension can be colloidal. The production of colloidalseed suspensions and their use in the synthesis of molecular sieves aredisclosed in, for example, International Publication Nos. WO 00/06493and WO 00/06494, both published on Feb. 10, 2000 and both of which areincorporated herein by reference.

Crystallization of the reaction mixture is carried out at either staticor stirred conditions in a suitable reactor vessel, such as for example,polypropylene jars or Teflon-lined or stainless steel autoclaves. In oneembodiment, the crystallization regime can involve heating the reactionmixture relatively quickly, at a rate of more than 10° C./hour,conveniently at least 15° C./hour or at least 20° C./hour, for examplefrom about 15° C./hour to about 150° C./hour or from about 20° C./hourto about 100° C./hour, to the desired crystallization temperature,typically between about 50° C. and about 250° C., for example from about150° C. to about 225° C. or from about 150° C. to about 200° C., such asfrom about 160° C. to about 195° C. (of course, in the first aspect ofthe invention, however, the desired crystallization temperature isadditionally at least 165° C., for example at least 170° C., and canoptionally also be not more than 190° C., for example not more than 185°C. or not more than 180° C.). In this embodiment, when the desiredcrystallization temperature is reached, the crystallization can beterminated immediately or from about 5 minutes to about 350 hours, andthe reaction mixture can be allowed to cool; additionally oralternately, the crystallization can run for at least about 12 hours,preferably at least about 16 hours, for example at least 24 hours, atleast 36 hours, at least 48 hours, at least 60 hours, at least 72 hours,at least 84 hours, at least 96 hours, at least 120 hours, or at least144 hours before cooling. Additionally in this embodiment, on cooling,the crystalline product can be recovered by standard means, such as bycentrifugation or filtration, then washed and dried.

In an alternate embodiment, the crystallization regime can involveheating the reaction mixture slowly, at a rate of less than 8° C./hour,conveniently at least 1° C./hour, such as from about 2° C./hour to about6° C./hour, to the desired crystallization temperature, typicallybetween about 50° C. and about 250° C., for example from about 150° C.to about 225° C. or from about 150° C. to about 200° C., such as fromabout 160° C. to about 195° C. (of course, in the first aspect of theinvention, however, the desired crystallization temperature isadditionally at least 165° C., for example at least 170° C., and canoptionally also be not more than 190° C., for example not more than 185°C. or not more than 180° C.). In this embodiment, when the desiredcrystallization temperature is reached, the crystallization can beterminated immediately or at least within less than 10 hours, such asless than 5 hours, and the reaction mixture can be allowed to cool.Additionally in this embodiment, on cooling, the crystalline product canbe recovered by standard means, such as by centrifugation or filtration,then washed and dried.

Optionally, the step of inducing crystallization can be done whilestirring.

In one embodiment of the first aspect of the invention, the crystallizedsilicoaluminophosphate molecular sieve has a crystal size distributionsuch that its average crystal size is less than 1.5 μm, preferably nomore than 1.2 μm, for example no more than 1.1 μm, no more than 1.0 μm,or no more than 0.9 μm.

As used herein, the term “average crystal size,” in reference to acrystal size distribution, should be understood to refer to ameasurement on a representative sample or an average of multiple samplesthat together form a representative sample. Average crystal size can bemeasured by SEM, in which case the crystal size of at least 30 crystalsmust be measured in order to obtain an average crystal size, and/oraverage crystal size can be measured by a laser light scatteringparticle size analyzer instrument, in which case the measured d₅₀ of thesample(s) can represent the average crystal size. It should also beunderstood that, while many of the crystals dealt with herein arerelatively uniform (for instance, very close to cubic, thus havinglittle difference between diameter measured along length, height, orwidth, e.g. when viewed in an SEM), the “average crystal size,” whenmeasured visually by SEM, represents the longest distance along one ofthe three-dimensional orthogonal axes (e.g., longest of length,width/diameter, and height, but not diagonal, in a cube, rectangle,parallelogram, ellipse, cylinder, frusto-cone, platelet, spheroid, orrhombus, or the like). However, the d₅₀, when measured by lightscattering in a particle size analyzer, is reported as a sphericalequivalent diameter, regardless of the shape and/or relative uniformityof shape of the crystals in each sample. In certain circumstances, thed₅₀ values measured by the particle size analyzer may not correspond,even roughly, to the average crystal size measured visually by arepresentative SEM micrograph. Often in these cases, the discrepancyrelates to an agglomeration of relatively small crystals that theparticle size analyzer interprets as a single particle. In suchcircumstances, where the d₅₀ values from the particle size analyzer andthe average crystal size from a representative SEM are significantlydifferent, the representative SEM micrograph should be the more accuratemeasure of “average crystal size.”

In a preferred embodiment, the order of addition of the components inthe mixture (i.e., in step (a)) can be important and can advantageouslybe tailored, e.g. to provide better homogeneity. For instance, step (a)can preferably comprise: (i) combining the source of phosphorus and thesource of aluminum, optionally with a liquid mixture medium, to form aprimary mixture; (ii) aging the primary mixture for an aging time andunder aging conditions (e.g., at an aging temperature), preferablysufficient to allow homogenization of the primary mixture,physico-chemical interaction between the source of phosphorus and thesource of aluminum, or both; and (iii) adding the source of silicon, theat least one organic template, and optionally additional liquid mixturemedium, to the aged primary mixture to form the synthesis mixture. Incertain cases of this embodiment, within step (iii), said source ofsilicon is combined with said primary mixture prior to adding said atleast one organic template (structure directing agent, or SDA).Advantageously, said primary mixture and said source of silicon can becombined to form a secondary mixture for a time and under conditions(e.g., temperature), preferably sufficient to allow homogenization ofthe secondary mixture, physico-chemical interaction between said sourceof silicon and said primary mixture, or both, after which said at leastone organic template is combined therewith.

When a component is added to a mixture to allow homogenization and/orphysico-chemical interaction, the aging time and temperature are two ofthe primary conditions. Although a variety of conditions can exist toallow sufficient contact for homogenization and/or interaction, in oneembodiment, when the aging temperature is somewhere between 0° C. and50° C., the aging time can advantageously be at least 5 minutes, forexample at least 10 minutes, at least 15 minutes, at least 20 minutes,at least 25 minutes, at least 30 minutes, at least 45 minutes, at least1 hour, or at least 2 hours. Again, when the aging temperature issomewhere between 0° C. and 50° C., the aging time does not really havea maximum, but can be up to 350 hours, for example up to 300 hours, upto 250 hours, up to 200 hours, up to 168 hours, up to 96 hours, up to 48hours, up to 24 hours, up to 16 hours, up to 12 hours, up to 8 hours, upto 6 hours, or up to 4 hours, depending on practical concerns relatingto synthesis timing, cost efficiency, manufacture schedules, or thelike.

Preferably, the Si/Al₂ ratio added to the synthesis mixture can be asclose as possible to the Si/Al₂ ratio of the crystallizedsilicoaluminophosphate molecular sieve (e.g. difference between theSi/Al₂ ratio in the synthesis mixture and in the crystallizedsilicoaluminophosphate molecular sieve can be no more than 0.10,preferably no more than 0.08, for example no more than 0.07) and/or thesynthesis mixture and the crystallized silicoaluminophosphate molecularsieve can both exhibit a relatively low Si/Al₂ ratio (e.g., both can beless than 0.33, preferably less than 0.30, for example no more than0.25, no more than 0.20, no more than 0.15, or no more than 0.10).

In a preferred embodiment according to the first aspect of theinvention, the crystallized silicoaluminophosphate molecular sieve isrecovered from step (b) in a yield that is at least 2.0% (e.g., at least2.5% or at least 3.0%) greater than a yield obtained by recovering asilicoaluminophosphate molecular sieve crystallized from an identicalsynthesis mixture at a crystallization temperature of 160° C. or lessfor a crystallization time from about 5 minutes to about 350 hours.

In a preferred embodiment of the invention, one or more of the followingare satisfied: the source of aluminum comprises alumina; the source ofphosphorus comprises phosphoric acid; the source of silicon can includean organosilicate comprising a tetra-alkylorthosilicate; and the atleast one organic template comprises N,N-dimethyl-cyclohexylamine.

In a preferred embodiment according to the first aspect of theinvention, the synthesis mixture exhibits a Si/Al₂ ratio less than 0.11,the crystallized silico-aluminophosphate molecular sieve exhibits aSi/Al₂ ratio less than 0.17, the crystallized silicoaluminophosphatemolecular sieve exhibits a Si/Al₂ ratio not more than 0.08 greater thanthe Si/Al₂ ratio of the synthesis mixture, said crystallizationtemperature is from 165° C. to 180° C., and the crystallizedsilicoaluminophosphate molecular sieve from step (c) has a crystal sizedistribution such that its average crystal size is not greater than 1.2μm.

In a preferred embodiment according to the second aspect of theinvention, the synthesis mixture exhibits a Si/Al₂ ratio less than 0.11,the crystallized silico-aluminophosphate molecular sieve exhibits aSi/Al₂ ratio less than 0.17, the crystallized silicoaluminophosphatemolecular sieve exhibits a Si/Al₂ ratio not more than 0.08 greater thanthe Si/Al₂ ratio of the synthesis mixture, and the crystallizationtemperature is between 150° C. and 200° C.

The product of the crystallization is an aluminophosphate orsilicoaluminophosphate containing a CHA framework-type molecular sievehaving an X-ray diffraction pattern including at least the d-spacingsshown in Table 1 below:

TABLE 1 Relative Intensities d(A) I/Io (%) 9.26 100 6.30 20 5.64 15 5.5157 4.96 25 4.92 27 4.29 76 4.18 21 3.55 32 3.50 20 3.42 10 2.91 22 2.8826 2.87 19

Although the crystallization product is normally a single phase CHAframework-type molecular sieve, in some cases the product may contain anintergrowth of a CHA framework-type molecular sieve with, for example anAEI framework-type molecular sieve or small amounts of other crystallinephases, such as APC and/or AFI framework-type molecular sieves. In oneembodiment, it is preferable for the crystallization product to have ashigh an amount of CHA framework type as possible, e.g., at least 95% CHAframework-type character, or even about 100% CHA framework-typecharacter (or as close as possible to single phase CHA framework-typecharacter as can currently be measured). Without being bound by theory,it is believed that silicoaluminophosphate molecular sieves havingincreased CHA framework-type character (and/or increased uniformity ofdistribution of silicon within the molecular sieve framework structure,i.e., decreased amounts of silicon islanding) can advantageously exhibitbetter performance (e.g., increased POS and optionally also POR, whichmeans prime olefin, or ethylene-to-propylene, ratio) inoxygenates-to-olefins conversion reactions, particularly inmethanol-to-olefins conversion reactions.

As a result of the crystallization process, the recovered crystallineproduct contains within its pores at least a portion of the organicdirecting agent used in the synthesis. In a preferred embodiment,activation is performed in such a manner that the organic directingagent is removed from the molecular sieve, leaving active catalyticsites within the microporous channels of the molecular sieve open forcontact with a feedstock. The activation process is typicallyaccomplished by calcining, or essentially heating the molecular sievecomprising the template at a temperature of from about 200° C. to about800° C. in the presence of an oxygen-containing gas. In some cases, itmay be desirable to heat the molecular sieve in an environment having alow or zero oxygen concentration. This type of process can be used forpartial or complete removal of the organic directing agent from theintracrystalline pore system.

Once the crystalline product has been activated, it can be formulatedinto a catalyst composition by combination with other materials, such asbinders and/or matrix materials, which provide additional hardness orcatalytic activity to the finished catalyst.

Materials which can be blended with the present molecular sieve materialinclude a large variety of inert and catalytically active materials.These materials include compositions such as kaolin and other clays,various forms of rare earth metals, other non-zeolite catalystcomponents, zeolite catalyst components, alumina or alumina sol,titania, zirconia, quartz, silica or silica sol, and mixtures thereof.These components are also effective in reducing overall catalyst cost,acting as a thermal sink to assist in heat shielding the catalyst duringregeneration, densifying the catalyst and increasing catalyst strength.When blended with such components, the amount of present CHA-containingcrystalline material contained in the final catalyst product ranges from10 to 90 weight percent of the total catalyst, preferably 20 to 80weight percent of the total catalyst.

The CHA framework type crystalline material produced by the presentprocess can be used to dry gases and liquids; for selective molecularseparation based on size and polar properties; as an ion-exchanger; as achemical carrier; in gas chromatography; and as a catalyst in organicconversion reactions. Examples of suitable catalytic uses of the CHAframework type crystalline material described herein include (a)hydrocracking of heavy petroleum residual feedstocks, cyclic stocks andother hydrocrackate charge stocks, normally in the presence of ahydrogenation component selected from Groups 6 and 8-10 of the PeriodicTable of Elements; (b) dewaxing, including isomerization dewaxing, toselectively remove straight chain paraffins from hydrocarbon feedstockstypically boiling above 177° C., including raffinates and lubricatingoil basestocks; (c) catalytic cracking of hydrocarbon feedstocks, suchas naphthas, gas oils, and residual oils, normally in the presence of alarge pore cracking catalyst, such as zeolite Y; (d) oligomerization ofstraight and branched chain olefins having from 2-21, preferably 2-5,carbon atoms, to produce medium to heavy olefins which are useful forboth fuels, e.g., gasoline or a gasoline blending stock, and chemicals;(e) isomerization of olefins, particularly olefins having 4-6 carbonatoms, and especially normal butene to produce iso-olefins; (f)upgrading of lower alkanes, such as methane, to higher hydrocarbons,such as ethylene and benzene; (g) disproportionation of alkylaromatichydrocarbons, such as toluene, to produce dialkylaromatic hydrocarbons,such as xylenes; (h) alkylation of aromatic hydrocarbons, such asbenzene, with olefins, such as ethylene and propylene, to producealkylated aromatics, such as ethylbenzene and cumene; (i) isomerizationof dialkylaromatic hydrocarbons, such as xylenes; (j) catalyticreduction of nitrogen oxides; and (k) synthesis of monoalkylamines anddialkylamines.

In particular, the CHA framework type crystalline material produced bythe present process is useful as a catalyst in the conversion ofoxygenates to one or more olefins, particularly ethylene and propylene.As used herein, the term “oxygenates” is defined to include, but is notnecessarily limited to, aliphatic alcohols, ethers, carbonyl compounds(aldehydes, ketones, carboxylic acids, carbonates, and the like), andalso compounds containing hetero-atoms, such as, halides, mercaptans,sulfides, amines, and mixtures thereof. The aliphatic moiety willnormally contain from 1-10 carbon atoms, such as from 1-4 carbon atoms.

Representative oxygenates include lower straight chain or branchedaliphatic alcohols, their unsaturated counterparts, and their nitrogen,halogen, and sulfur analogues. Examples of suitable oxygenate compoundscan include, but are not necessarily limited to: methanol; ethanol;n-propanol; isopropanol; C₄ to C₁₀ alcohols; methyl ethyl ether;dimethyl ether; diethyl ether; di-isopropyl ether; methyl mercaptan;methyl sulfide; methyl amine; ethyl mercaptan; di-ethyl sulfide;di-ethyl amine; ethyl chloride; formaldehyde; di-methyl carbonate;di-methyl ketone; acetic acid; n-alkyl amines; n-alkyl halides; n-alkylsulfides having n-alkyl groups comprising from 3-10 carbon atoms; andthe like; and mixtures thereof. Particularly suitable oxygenatecompounds are methanol, dimethyl ether, and mixtures thereof, and mostpreferably comprise methanol. As used herein, the term “oxygenate”designates only the organic material used as the feed. The total chargeof feed to the reaction zone may contain additional compounds, such asdiluents.

In one embodiment of the oxygenate conversion process, a feedstockcomprising an organic oxygenate, optionally with one or more diluents,is contacted in the vapor phase in a reaction zone with a catalystcomprising the present molecular sieve at effective process conditionsso as to produce the desired olefins. Alternatively, the process may becarried out in a liquid or a mixed vapor/liquid phase. When the processis carried out in the liquid phase or a mixed vapor/liquid phase,different conversion rates and selectivities of feedstock-to-product mayresult depending upon the catalyst and the reaction conditions.

When present, the diluent(s) is(are) generally non-reactive to thefeedstock or molecular sieve catalyst composition and is typically usedto reduce the concentration of the oxygenate in the feedstock.Non-limiting examples of suitable diluents include helium, argon,nitrogen, carbon monoxide, carbon dioxide, water, essentiallynon-reactive paraffins (especially alkanes such as methane, ethane, andpropane), essentially non-reactive aromatic compounds, and mixturesthereof. The most preferred diluents include water and nitrogen, withwater being particularly preferred. Diluent(s) may comprise from about 1mol % to about 99 mol % of the total feed mixture.

The temperature employed in the oxygenate conversion process may varyover a wide range, such as from about 200° C. to about 1000° C., forexample from about 250° C. to about 800° C., including from about 250°C. to about 750° C., conveniently from about 300° C. to about 650° C.,typically from about 350° C. to about 600° C. and particularly fromabout 400° C. to about 600° C.

Light olefin products will form, although not necessarily in optimumamounts, at a wide range of pressures, including but not limited toautogenous pressures and pressures in the range from about 0.1 kPa toabout 10 MPa. Conveniently, the pressure can be in the range from about7 kPa to about 5 MPa, such as from about 50 kPa to about 1 MPa. Theforegoing pressures are exclusive of diluents, if any are present, andrefer to the partial pressure of the feedstock as it relates tooxygenate compounds and/or mixtures thereof. Lower and upper extremes ofpressure may adversely affect selectivity, conversion, coking rate,and/or reaction rate; however, light olefins such as ethylene and/orpropylene still may form.

In a preferred embodiment, the method of converting hydrocarbons intoolefins according to the invention comprises: (a) preparing asilicoaluminophosphate molecular sieve according to the methodsdisclosed hereinabove; (b) formulating said silicoaluminophosphatemolecular sieve, along with a binder and optionally a matrix material,into a silicoaluminophosphate molecular sieve catalyst composition,typically comprising from at least 10% to about 50% molecular sieve; and(c) contacting said catalyst composition with a hydrocarbon feed underconditions sufficient to convert said hydrocarbon feed into a productcomprising predominantly one or more olefins, preferably to attain aprime olefin selectivity of at least 70 wt % (as measured at about 500°C.). Preferably, the hydrocarbon feed is an oxygenate-containing feedcomprising methanol, dimethylether, or a combination thereof, and theone or more olefins typically comprises ethylene, propylene, or acombination thereof.

A wide range of weight hourly space velocities (WHSV) for the feedstockwill function in the oxygenate conversion process. WHSV is defined asweight of feed (excluding diluents) per hour per weight of a totalreaction volume of molecular sieve catalyst (excluding inert and/orfillers). The WHSV generally should be in the range from about 0.01 hr⁻¹to about 500 hr⁻¹, such from about 0.5 hr⁻¹ to about 300 hr⁻¹, forexample from about 0.1 hr⁻¹ to about 200 hr⁻¹.

A practical embodiment of a reactor system for the oxygenate conversionprocess is a circulating fluid bed reactor with continuous regeneration.Fixed beds are generally not preferred for the process, becauseoxygenate-to-olefin conversion is a highly exothermic process thatrequires several stages with intercoolers or other cooling devices. Thereaction also results in a high pressure drop, due to the production oflow pressure, low density gas.

Because the catalyst typically needs to be regenerated frequently, thereactor should preferably allow easy removal of at least a portion ofthe catalyst to a regenerator, where the catalyst can be subjected to aregeneration medium, such as a gas comprising oxygen, for example air,to burn off coke from the catalyst, which should restore at least someof the catalyst activity. The conditions of temperature, oxygen partialpressure, and residence time in the regenerator can typically beselected to achieve a coke content on regenerated catalyst of less thanabout 1 wt %, for example less than about 0.5 wt %. At least a portionof the regenerated catalyst should be returned to the reactor.

In a preferred embodiment, the method of forming an olefin-based polymerproduct comprises: (a) preparing a silicoaluminophosphate molecularsieve according to the methods described hereinabove; (b) formulatingsaid silicoaluminophosphate molecular sieve, along with a binder andoptionally a matrix material, into a silicoaluminophosphate molecularsieve catalyst composition comprising from at least 10% to about 50%molecular sieve; (c) contacting said catalyst composition with ahydrocarbon feed under conditions sufficient to convert said hydrocarbonfeed into a product comprising predominantly one or more olefins; and(d) polymerizing at least one of the one or more olefins, optionallywith one or more other comonomers and optionally (but preferably) in thepresence of a polymerization catalyst, under conditions sufficient toform an olefin-based (co)polymer. Preferably, in this preferredembodiment, the hydrocarbon feed is an oxygenate-containing feedcomprising methanol, dimethylether, or a combination thereof, the one ormore olefins typically comprises ethylene, propylene, or a combinationthereof, and the olefin-based (co)polymer is an ethylene-containing(co)polymer, a propylene-containing (co)polymer, or a copolymer,mixture, or blend thereof.

Additionally or alternately, the invention can be described by thefollowing embodiments.

Embodiment 1

A method of preparing a silicoaluminophosphate molecular sieve having acontrolled acid site density, the method comprising: (a) providing asynthesis mixture comprising a source of aluminum, a source ofphosphorus, a source of silicon, and at least one organic templatecontaining (i) a 4- to 8-membered cycloalkyl group, optionallysubstituted by 1-3 alkyl groups having from 1-3 carbon atoms, or (ii) a4- to 8-membered heterocyclic group having from 1-3 heteroatoms, saidheterocyclic group being optionally substituted by 1-3 alkyl groupshaving from 1-3 carbon atoms, and said heteroatoms in said heterocyclicgroups being selected from the group consisting of O, N, and S, whereinthe synthesis mixture exhibits a Si/Al₂ ratio less than 0.33; and (b)inducing crystallization of a silicoaluminophosphate molecular sieve,which exhibits 90% or greater CHA framework type character, from saidsynthesis mixture at a crystallization temperature of at least 165° C.for a crystallization time from about 5 minutes to about 350 hours,wherein (i) the crystallized silicoaluminophosphate molecular sieveexhibits a Si/Al₂ ratio less than 0.33, (ii) the crystallizedsilicoaluminophosphate molecular sieve exhibits a Si/Al₂ ratio not morethan 0.10 greater than the Si/Al₂ ratio of the synthesis mixture, or(iii) both (i) and (ii).

Embodiment 2

A method of preparing a silicoaluminophosphate molecular sieve having adesired crystal size, the method comprising: (a) combining a source ofphosphorus and a source of aluminum, optionally with a liquid mixturemedium, to form a primary mixture; (b) aging the primary mixture for anaging time and under aging conditions sufficient to allow homogenizationof the primary mixture, physico-chemical interaction between the sourceof phosphorus and the source of aluminum, or both; (c) adding a sourceof silicon, at least one organic template, and optionally additionalliquid mixture medium, to the aged primary mixture to form a synthesismixture; and (d) inducing crystallization of a silicoaluminophosphatemolecular sieve, which exhibits 90% or greater CHA framework typecharacter, from said synthesis mixture at a crystallization temperature,wherein the at least one organic template contains (i) a 4- to8-membered cycloalkyl group, optionally substituted by 1-3 alkyl groupshaving from 1-3 carbon atoms, or (ii) a 4- to 8-membered heterocyclicgroup having from 1-3 heteroatoms, said heterocyclic group beingoptionally substituted by 1-3 alkyl groups having from 1-3 carbon atoms,and said heteroatoms in said heterocyclic groups being selected from thegroup consisting of O, N, and S, wherein the synthesis mixture and thecrystallized silicoaluminophosphate molecular sieve both exhibit aSi/Al₂ ratio less than 0.33, and wherein the crystallizedsilicoaluminophosphate molecular sieve has a crystal size distributionsuch that its average crystal size is not greater than 3.0 μm.

Embodiment 3

The method of embodiment 1 or embodiment 2, wherein the synthesismixture exhibits a Si/Al₂ ratio less than 0.17, and wherein thecrystallized silicoaluminophosphate molecular sieve exhibits a Si/Al₂ratio less than 0.25.

Embodiment 4

The method of any of the previous embodiments, wherein step (b) is donewhile stirring.

Embodiment 5

The method of any of the previous embodiments, wherein the at least oneorganic template contains a cyclohexyl group, optionally substituted by1 to 3 methyl groups.

Embodiment 6

The method of embodiment 5, wherein the at least one organic templatecomprises N,N-dimethylcyclohexylamine.

Embodiment 7

The method any of embodiments 1-5, wherein one or more of the followingare satisfied: the source of aluminum comprises alumina; the source ofphosphorus comprises phosphoric acid; the source of silicon comprises atetraalkylorthosilicate; and the at least one organic template comprisesN,N-dimethylcyclohexylamine.

Embodiment 8

The method of any of the previous embodiments, wherein step (b) wasaccomplished using seeds having a framework type of CHA, AEI, AFX, LEV,an intergrowth thereof, or a combination thereof.

Embodiment 9

The method of any of the previous embodiments, wherein the crystallizedsilicoaluminophosphate molecular sieve exhibits a Si/Al₂ ratio not morethan 100% greater than the Si/Al₂ ratio of the synthesis mixture.

Embodiment 10

The method of any of the previous embodiments, wherein saidcrystallization temperature is from 170° C. to 200° C.

Embodiment 11

The method of any of embodiments 1 and 3-10, wherein the crystallizedsilicoaluminophosphate molecular sieve from step (b) has a crystal sizedistribution such that its average crystal size is not greater than 1.2μm.

Embodiment 12

The method of any of embodiments 1 and 3-11, wherein the crystallizedand treated silicoaluminophosphate molecular sieve is recovered fromstep (b) in a yield that is at least 2.0% greater than a yield obtainedby recovering a silicoaluminophosphate molecular sieve crystallized froman identical synthesis mixture at a crystallization temperature of 160°C. or less for a crystallization time from about 5 minutes to about 350hours.

Embodiment 13

The method of any of embodiments 1 and 3-12, wherein: the synthesismixture exhibits a Si/Al₂ ratio less than 0.11, the crystallizedsilicoaluminophosphate molecular sieve exhibits a Si/Al₂ ratio less than0.17, the crystallized silicoaluminophosphate molecular sieve exhibits aSi/Al₂ ratio not more than 0.08 greater than the Si/Al₂ ratio of thesynthesis mixture, the crystallization temperature is between 165° C.and 180° C., and the crystallized silicoaluminophosphate molecular sievefrom step (b) has a crystal size distribution such that its averagecrystal size is not greater than 1.2 μm.

Embodiment 14

The method of any of embodiments 1-12, wherein the crystallizedsilicoaluminophosphate molecular sieve exhibits a Si/Al₂ ratio not morethan 0.10 greater than the Si/Al₂ ratio of the synthesis mixture.

Embodiment 15

The method of any of embodiments 2-9, 11, and 14, wherein thecrystallization temperature is between 150° C. and 200° C.

Embodiment 16

The method of any of embodiments 2-15, wherein, within step (c), saidsource of silicon is combined with said primary mixture prior to addingsaid at least one organic template.

Embodiment 17

The method of embodiment 16, wherein said primary mixture and saidsource of silicon are combined to form a secondary mixture for a timeand under conditions sufficient to allow homogenization of the secondarymixture, physico-chemical interaction between said source of silicon andsaid primary mixture, or both, after which said at least one organictemplate is combined therewith.

Embodiment 18

The method of any of embodiments 2-17, wherein the aging time is atleast 15 minutes at aging temperatures between 0° C. and 50° C.

Embodiment 19

The method of any of embodiments 2-9, 14, and 16-18, wherein: thesynthesis mixture exhibits a Si/Al₂ ratio less than 0.11, thecrystallized silicoaluminophosphate molecular sieve exhibits a Si/Al₂ratio less than 0.17, the crystallized silicoaluminophosphate molecularsieve exhibits a Si/Al₂ ratio not more than 0.08 greater than the Si/Al₂ratio of the synthesis mixture, and the crystallization temperature isbetween 150° C. and 200° C.

Embodiment 20

A method of converting hydrocarbons into olefins comprising: (a)preparing a silicoaluminophosphate molecular sieve according to themethod of any of the previous embodiments; (b) formulating saidsilicoaluminophosphate molecular sieve, along with a binder andoptionally a matrix material, into a silicoaluminophosphate molecularsieve catalyst composition comprising from at least 10% to about 50%molecular sieve; and (c) contacting said catalyst composition with ahydrocarbon feed under conditions sufficient to convert said hydrocarbonfeed into a product comprising predominantly one or more olefins.

Embodiment 21

The method of embodiment 20, wherein the hydrocarbon feed is anoxygenate-containing feed comprising methanol, dimethylether, or acombination thereof, and wherein the one or more olefins comprisesethylene, propylene, or a combination thereof.

Embodiment 22

A method of forming an olefin-based polymer product comprising: (a)preparing a silicoaluminophosphate molecular sieve according to themethod of any of embodiments 1-19; (b) formulating saidsilicoaluminophosphate molecular sieve, along with a binder andoptionally a matrix material, into a silicoaluminophosphate molecularsieve catalyst composition comprising from at least 10% to about 50%molecular sieve; (c) contacting said catalyst composition with ahydrocarbon feed under conditions sufficient to convert said hydrocarbonfeed into a product comprising predominantly one or more olefins; (d)polymerizing at least one of the one or more olefins, optionally withone or more other comonomers and optionally in the presence of apolymerization catalyst, under conditions sufficient to form anolefin-based (co)polymer.

Embodiment 23

The method of embodiment 22, wherein the hydrocarbon feed is anoxygenate-containing feed comprising methanol, dimethylether, or acombination thereof, wherein the one or more olefins comprises ethylene,propylene, or a combination thereof, and wherein the olefin-based(co)polymer is an ethylene-containing (co)polymer, apropylene-containing (co)polymer, or a copolymer, mixture, or blendthereof.

The invention will now be more particularly described with reference tothe following Examples and the accompanying drawings.

EXAMPLES

The analysis techniques described below were among those used incharacterizing various samples from the Examples.

ICP-OES

Elemental analysis has been done using ICP-OES (Inductively CoupledPlasma-Optical Emission Spectrometry). Samples were dissolved in amixture of acids and diluted in deionized water. The instrument(Simultaneous VISTA-MPX from Varian) was calibrated using commercialavailable standards (typically at least 3 standards and a blank). Thepower used was about 1.2 kW, plasma flow about 13.5 L/min, and nebulizerpressure about 200 kPa for all lines. Results are expressed in wt % orppm by weight (wppm), and the values are recalculated to Si/Al₂ molarratios.

XRD

Either of two X-ray diffractometers was used: a STOE Stadi-P CombiTransmission XRD and a Scintag X2 Reflection XRD with optional samplerotation. Cu—K_(α) radiation was used. Typically, a step size of 0.2° 2Θand a measurement time of about 1 hour were used.

SEM

A JEOL JSM-6340F Field-Emission-Gun scanning electron microscope (SEM)was used, operating at about 2 kV and about 12 μA. Prior to measurement,samples were dispersed in ethanol, subjected to ultrasonic treatment forabout 5 to about 30 minutes, deposited on SEM sample holders, and driedat room temperature and pressure (about 20-25° C. and about 101 kPa). Ifan average particle size was determined based on the SEM micrographs,typically the measurement was performed on at least 30 crystals. In caseof the near cubic crystals, the average was based on the sizes of one ofthe edges of each crystal.

PSA

Particle size analysis was performed using a Mastersizer APA2000 fromMalvern Instruments Limited, equipped with a 4 mW laser beam, based onlaser scattering by randomly moving particles in a liquid medium. Thesamples to be measured were dispersed in water under continuousultrasonic treatment to ensure proper dispersion. The pump speed appliedwas 2000 RPM, and the stirrer speed was 800 RPM. The parameters used inthe operation procedure were: Refractive Index=1.544, Absorption=0.1.The results were calculated using the “general purpose-enhancedsensitivity” model. The results were expressed as d₅₀, meaning that 50vol % of the particles were smaller than the value. The average of atleast 2 measurements, with a delay of at least about 10 seconds, wasreported.

Comparative Examples A-H

For Comparative Example A, a synthesis mixture having a molarcomposition of about 0.02 SiO₂:P₂O₅:Al₂O₃:2 DMCHA:40H₂O, as well as 100wt ppm seeds, was prepared according to the following procedure. Asolution of phosphoric acid was prepared by combining phosphoric acid[Acros 85%] and water. To this solution was added the appropriate amountof Condea Pural SB [Sasol, 75.6 wt % Al₂O₃] and the slurry was stirredfor about 1 hour at about 10° C. To this mixture was added theappropriate amount of TEOS [tetraethyorthosilicate from Aldrich, 98%].This mixture was then aged at about 10° C. while stirring for aboutanother one hour. Then the appropriate amount of dimethylcyclohexylamine[DMCHA from Purum Fluka] was added. This mixture was stirred for about10 minutes before the seeds (SAPO-34 seeds) were added. The finalmixture was transferred to an autoclave which was stirred and heated toabout 160° C. with a heat-up rate of about 40° C./hr, while stirring,and was kept under these conditions for about 144 hours. After thistime, the autoclave was cooled to approximately room temperature (about20-25° C.), and the solids were washed with demineralized water anddried at about 120° C. The phase purity of the sample was determined byX-ray diffraction and was characterized substantially by the d-spacingsshown in Table 1 above. The yield was determined by weighing the driedsolids and dividing this weight by the weight of the initial synthesismixture. The so-calculated yield was about 2.8 wt %. SEM micrographswere recorded, and the crystal size was determined to be, on average,approximately 1.0 μm. The Si/Al₂ ratio in the recovered product wasdetermined to be about 0.13.

A series of samples was made according to the same procedure, onlychanging the Si/Al₂ ratio of the synthesis mixture (Comparative ExamplesB-H). All of these remaining product samples were determined to becharacterized substantially by the d-spacings shown in Table 1 above,with an average crystal size, d₅₀, smaller than 1 μm. The various Si/Al₂ratios in the recovered product and the yields are summarized in Table 2below.

TABLE 2 Yield, d₅₀, and Si/Al₂ ratio in products crystallized at about160° C., based on various Si/Al₂ ratios in the synthesis mixture. Comp.Ex. Si/Al₂ in mix. Yield % Si/Al₂ in prod. d₅₀ [μm] A 0.02 2.8 0.13 1.0B 0.04 3.6 0.17 0.5 C 0.06 4.6 0.21 0.4 D 0.08 6.8 0.21 0.6 E 0.10 8.50.21 0.9 F 0.12 7.4 0.25 0.5 G 0.14 9.5 0.27 0.5 H 0.15 9.5 0.29 0.5

Examples 1-8

A similar series of synthesis mixtures as in Comparative Examples A-Hwas subjected to crystallization at about 170° C. under stirredconditions for about 24 hours, with all other parameters of theComparative Examples remaining the same. The results are summarized inTable 3 below.

TABLE 3 Yield, d₅₀, and Si/Al₂ ratio in products crystallized at about170° C., based on various Si/Al₂ ratios in the synthesis mixture.Example Si/Al₂ in mix. Yield % Si/Al₂ in prod. d₅₀ [μm] 1 0.02 9.6 0.030.9 2 0.04 9.7 0.07 0.8 3 0.06 10.2 0.09 0.7 4 0.08 10.3 0.14 0.8 5 0.1010.8 0.15 0.6 6 0.12 10.5 0.19 0.6 7 0.14 11.6 0.22 0.8 8 0.15 11.8 0.230.7

The graphical results of the Examples and the Comparative Examples fromTables 2 and 3, with some additional data that are either repeats of thesame Si/Al ratio as shown in the examples or an extension of Si/Alration into higher values, are shown in attached FIGS. 1 and 2.

From these results it can be concluded that, in order to obtainmolecular sieve catalyst materials (e.g., such as characterizedsubstantially by the d-spacings shown in Table 1 above) with relativelylow Si/Al₂ molar ratios (e.g., below 0.10) in the product, ahydrothermal treatment at a temperature above the crystallizationtemperature can preferably be undertaken and/or the crystallizationtemperature can preferably be greater than about 160° C. The yields ofthe products made using such higher temperatures have also been shown tobe higher, even despite relatively shorter crystallization/treatmenttimes.

Comparative Example I

A synthesis mixture having a molar composition of about 0.03SiO₂:P₂O_(5:)Al₂O₃:2 DMCHA:40H₂O, as well as 100 wt ppm seeds (SAPO-34seeds), was prepared according to the following procedure. Theappropriate amount of the silicon source, TEOS [tetraethyorthosilicatefrom Aldrich, 98%], was added to a dilute solution of phosphoric acid[prepared from a mixture of water and 85% phosphoric acid from Acros],in order to sufficiently disperse the silicon source in the liquid. Tothis solution was added the appropriate amount of Condea Pural SB[Sasol, 74.2 wt % Al₂O₃] as the alumina source. The resulting mixturewas stirred for about 10 minutes before the appropriate amount ofdimethylcyclohexylamine [DMCHA from Purum Fluka] template was added.This resulting slurry/mixture was stirred for about another 10 minutesbefore the seeds (SAPO-34 seeds) were added, after which the finalmixture was homogenized for about another 10 minutes before being loadedinto a reactor vessel. The final mixture was stirred and heated to about170° C. with a heat-up rate of about 5° C./hr, and was kept under theseconditions for about 120 hours. After this time, the reaction mixturewas cooled to approximately room temperature, and the solids wereseparated from the mother liquor, washed with demineralized water, anddried at about 120° C. The yield was determined by weighing the driedsolids and dividing this weight by the weight of the initial synthesismixture. The so-calculated yield was about 9.7 wt %. The phase purity ofthe sample was determined by X-ray diffraction and was characterizedsubstantially by the d-spacings shown in Table 1 above. The d₅₀, asdetermined by PSA, was approximately 4.9 μm. The Si/Al₂ ratio of theproduct, as determined by ICP after dissolution of the crystals, wasabout 0.14. The SEM of the product is shown in FIG. 3.

The mixing procedure of Comparative Example I, though resulting inrelatively well-dispersed silicon, did not result in small crystals andexhibited an unacceptably high silicon incorporation level, despite thelow initial Si/Al₂ molar ratio of the initial synthesis mixture.

Comparative Example J

A synthesis mixture having a molar composition of about 0.03SiO₂:P₂O_(5:)Al₂O₃:2 DMCHA:40H₂O, as well as 100 wt ppm seeds (SAPO-34seeds), was prepared according to the following procedure. A solution ofphosphoric acid was prepared by combining phosphoric acid [Acros 85%]and water. To this solution was added the appropriate amount of CondeaPural SB [Sasol, 74.2 wt % Al₂O₃] and the slurry was stirred for about10 minutes. To this mixture was added the appropriate amount of TEOS[tetraethyorthosilicate from Aldrich, 98%]. Then the appropriate amountof dimethylcyclohexylamine [DMCHA from Purum Fluka] template was added.This mixture was stirred for about 10 minutes before the seeds wereadded. The final mixture was transferred to an autoclave which washeated to about 170° C. with a heat-up rate of about 5° C./hr, whilestirring, and was kept under these conditions for about 100 hours. Afterthis time, the autoclave was cooled to approximately room temperature,and the solids were washed with demineralized water and dried at about120° C. The yield was determined by weighing the dried solids anddividing this weight by the weight of the initial synthesis mixture. Theso-calculated yield was about 15.1 wt %. The phase purity of the samplewas determined by X-ray diffraction and was characterized substantiallyby the d-spacings shown in Table 1 above. The d₅₀, as determined by PSA,was approximately 4.1 μm. The Si/Al₂ ratio of the product, as determinedby ICP-OES after dissolution of the crystals, was about 0.03. The SEM ofthe product is shown in FIG. 4.

The mixing procedure of Comparative Example J, like Comparative ExampleI, resulted in relatively large crystals. Unlike Comparative Example I,Comparative Example J exhibited not only relatively high yield, but alsoan accurate (low) silicon incorporation level, in line with the lowinitial Si/Al₂ molar ratio of the initial synthesis mixture.

Example 9

A synthesis mixture having a molar composition of about 0.03SiO₂:P₂O_(5:)Al₂O₃:2 DMCHA:40H₂O, as well as 100 wt ppm seeds, wasprepared according to the following procedure. A solution of phosphoricacid was prepared by combining phosphoric acid [Acros 85%] and water. Tothis solution was added the appropriate amount of Condea Pural SB[Sasol, 74.2 wt % Al₂O₃] and the slurry was stirred for about 1 hour atabout 35° C. To this mixture was added the appropriate amount of TEOS[tetraethyorthosilicate from Aldrich]. Then the appropriate amount ofdimethylcyclohexylamine [DMCHA from Purum Fluka] was added. This mixturewas stirred for about 10 minutes before the seeds (SAPO-34 seeds) wereadded. The final mixture was transferred to an autoclave which wasstirred and heated to about 170° C. with a heat-up rate of about 5°C./hr, while stirring, and was kept under these conditions for about 120hours. After this time, the autoclave was cooled to approximately roomtemperature, and the solids were washed with demineralized water anddried at about 120° C. The yield was determined by weighing the driedsolids and dividing this weight by the weight of the initial synthesismixture. The so-calculated yield was about 9.2 wt %. The phase purity ofthe sample was determined by X-ray diffraction and was characterizedsubstantially by the d-spacings shown in Table 1 above. The d₅₀, asdetermined by PSA, was approximately 2.7 μm. The Si/Al₂ ratio of theproduct, as determined by ICP-OES after dissolution of the crystals, wasabout 0.08. The SEM of the product is shown in FIG. 5.

In examining the aforementioned Comparative Examples I-J and Example 9,it can be seen that the preferred mixing procedure (e.g. the sequence ofaddition, as well as aging times) according to the invention canadvantageously result in crystals of molecular sieve material having asmaller average crystal diameter (d₅₀) and a lower Si/Al₂ ratio in theproduct sieve.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For this reason, then, reference shouldbe made solely to the appended claims for purposes of determining thetrue scope of the present invention.

1. A method of preparing a silicoaluminophosphate molecular sieve havinga controlled acid site density, the method comprising: (a) providing asynthesis mixture comprising a source of aluminum, a source ofphosphorus, a source of silicon, and at least one organic templatecontaining (i) a 4- to 8-membered cycloalkyl group, optionallysubstituted by 1-3 alkyl groups having from 1-3 carbon atoms, or (ii) a4- to 8-membered heterocyclic group having from 1-3 heteroatoms, saidheterocyclic group being optionally substituted by 1-3 alkyl groupshaving from 1-3 carbon atoms, and said heteroatoms in said heterocyclicgroups being selected from the group consisting of O, N, and S, whereinthe synthesis mixture exhibits a Si/Al₂ ratio less than 0.33; and (b)inducing crystallization of a silicoaluminophosphate molecular sieve,which exhibits 90% or greater CHA framework type character, from saidsynthesis mixture at a crystallization temperature of at least 165° C.for a crystallization time from about 5 minutes to about 350 hours,wherein (i) the crystallized silicoaluminophosphate molecular sieveexhibits a Si/Al₂ ratio less than 0.33, (ii) the crystallizedsilicoaluminophosphate molecular sieve exhibits a Si/Al₂ ratio not morethan 0.10 greater than the Si/Al₂ ratio of the synthesis mixture, or(iii) both (i) and (ii).
 2. The method of claim 1, wherein the synthesismixture exhibits a Si/Al₂ ratio less than 0.17, and wherein thecrystallized silicoaluminophosphate molecular sieve exhibits a Si/Al₂ratio less than 0.25.
 3. The method of claim 2, wherein the crystallizedsilicoaluminophosphate molecular sieve exhibits a Si/Al₂ ratio not morethan 100% greater than the Si/Al₂ ratio of the synthesis mixture.
 4. Themethod of claim 1, wherein step (b) is done while stirring.
 5. Themethod of claim 2, wherein said crystallization temperature is from 170°C. to 200° C.
 6. The method of claim 1, wherein the at least one organictemplate contains a cyclohexyl group, optionally substituted by 1 to 3methyl groups.
 7. The method of claim 6, wherein the at least oneorganic template comprises N,N-dimethylcyclohexylamine.
 8. The method ofclaim 1, wherein the crystallized silicoaluminophosphate molecular sievefrom step (c) has a crystal size distribution such that the averagecrystal size is not greater than 1.2 μm.
 9. The method of claim 1,wherein the crystallized silicoaluminophosphate molecular sieve isrecovered from step (b) in a yield that is at least 2.0% greater than ayield obtained by recovering a silicoaluminophosphate molecular sievecrystallized from an identical synthesis mixture at a crystallizationtemperature of 160° C. or less for a crystallization time from about 5minutes to about 350 hours.
 10. The method of claim 1, wherein one ormore of the following are satisfied: the source of aluminum comprisesalumina; the source of phosphorus comprises phosphoric acid; the sourceof silicon comprises a tetraalkylorthosilicate; and the at least oneorganic template comprises N,N-dimethylcyclohexylamine.
 11. The methodof claim 1, wherein step (b) was accomplished using seeds having aframework type of CHA, AEI, AFX, LEV, an intergrowth thereof, or acombination thereof.
 12. The method of claim 1, wherein: the synthesismixture exhibits a Si/Al₂ ratio less than 0.11, the crystallizedsilicoaluminophosphate molecular sieve exhibits a Si/Al₂ ratio less than0.17, the crystallized silicoaluminophosphate molecular sieve exhibits aSi/Al₂ ratio not more than 0.08 greater than the Si/Al₂ ratio of thesynthesis mixture, the crystallization temperature is between 165° C.and 180° C., and the crystallized silicoaluminophosphate molecular sievefrom step (b) has a crystal size distribution such that the averagecrystal size is not greater than 1.2 μm.
 13. A method of convertinghydrocarbons into olefins comprising: (a) preparing asilicoaluminophosphate molecular sieve according to the method of claim1; (b) formulating said silicoaluminophosphate molecular sieve, alongwith a binder and optionally a matrix material, into asilicoaluminophosphate molecular sieve catalyst composition comprisingfrom at least 10% to about 50% molecular sieve; and (c) contacting saidcatalyst composition with a hydrocarbon feed under conditions sufficientto convert said hydrocarbon feed into a product comprising predominantlyone or more olefins.
 14. The method of claim 13, wherein the hydrocarbonfeed is an oxygenate-containing feed comprising methanol, dimethylether,or a combination thereof, and wherein the one or more olefins comprisesethylene, propylene, or a combination thereof.
 15. A method of formingan olefin-based polymer product comprising: (a) preparing asilicoaluminophosphate molecular sieve according to the method of claim1; (b) formulating said silicoaluminophosphate molecular sieve, alongwith a binder and optionally a matrix material, into asilicoaluminophosphate molecular sieve catalyst composition comprisingfrom at least 10% to about 50% molecular sieve; (c) contacting saidcatalyst composition with a hydrocarbon feed under conditions sufficientto convert said hydrocarbon feed into a product comprising predominantlyone or more olefins; (d) polymerizing at least one of the one or moreolefins, optionally with one or more other comonomers and optionally inthe presence of a polymerization catalyst, under conditions sufficientto form an olefin-based (co)polymer.
 16. The method of claim 15, whereinthe hydrocarbon feed is an oxygenate-containing feed comprisingmethanol, dimethylether, or a combination thereof, wherein the one ormore olefins comprises ethylene, propylene, or a combination thereof,and wherein the olefin-based (co)polymer is an ethylene-containing(co)polymer, a propylene-containing (co)polymer, or a copolymer,mixture, or blend thereof.
 17. A method of preparing asilicoaluminophosphate molecular sieve having a desired crystal size,the method comprising: (a) combining a source of phosphorus and a sourceof aluminum, optionally with a liquid mixture medium, to form a primarymixture; (b) aging the primary mixture for an aging time and under agingconditions sufficient to allow homogenization of the primary mixture,physico-chemical interaction between the source of phosphorus and thesource of aluminum, or both; (c) adding a source of silicon, at leastone organic template, and optionally additional liquid mixture medium,to the aged primary mixture to form a synthesis mixture; and (d)inducing crystallization of a silicoaluminophosphate molecular sieve,which exhibits 90% or greater CHA framework type character, from saidsynthesis mixture at a crystallization temperature, wherein the at leastone organic template contains (i) a 4- to 8-membered cycloalkyl group,optionally substituted by 1-3 alkyl groups having from 1-3 carbon atoms,or (ii) a 4- to 8-membered heterocyclic group having from 1-3heteroatoms, said heterocyclic group being optionally substituted by 1-3alkyl groups having from 1-3 carbon atoms, and said heteroatoms in saidheterocyclic groups being selected from the group consisting of O, N,and S, wherein the synthesis mixture and the crystallizedsilicoaluminophosphate molecular sieve both exhibit a Si/Al₂ ratio lessthan 0.33, and wherein the crystallized silicoaluminophosphate molecularsieve has a crystal size distribution such that its average crystal sizeis not greater than 3.0 μm.
 18. The method of claim 17, wherein thesynthesis mixture exhibits a Si/Al₂ ratio less than 0.11, and whereinthe crystallized silicoaluminophosphate molecular sieve exhibits aSi/Al₂ ratio less than 0.17.
 19. The method of claim 17, wherein thecrystallized silicoaluminophosphate molecular sieve exhibits a Si/Al₂ratio not more than 0.10 greater than the Si/Al₂ ratio of the synthesismixture.
 20. The method of claim 17, wherein inducing step is done whilestirring.
 21. The method of claim 17, wherein the crystallizationtemperature is between 150° C. and 200° C.
 22. The method of claim 17,wherein, within step (c), said source of silicon is combined with saidprimary mixture prior to adding said at least one organic template. 23.The method of claim 22, wherein said primary mixture and said source ofsilicon are combined to form a secondary mixture for a time and underconditions sufficient to allow homogenization of the secondary mixture,physico-chemical interaction between said source of silicon and saidprimary mixture, or both, after which said at least one organic templateis combined therewith.
 24. The method of claim 17, wherein the at leastone organic template comprises N,N-dimethylcyclohexylamine.
 25. Themethod of claim 17, wherein the aging time is at least 15 minutes ataging temperatures between 0° C. and 50° C.
 26. The method of claim 17,wherein one or more of the following are satisfied: the source ofaluminum comprises alumina; the source of phosphorus comprisesphosphoric acid; the source of silicon comprises atetraalkylorthosilicate; and the at least one organic template comprisesN,N-dimethylcyclohexylamine.
 27. The method of claim 17, whereincrystallization was accomplished using seeds having a framework type ofCHA, AEI, AFX, LEV, an intergrowth thereof, or a combination thereof.28. The method of claim 17, wherein: the synthesis mixture exhibits aSi/Al₂ ratio less than 0.11, the crystallized silicoaluminophosphatemolecular sieve exhibits a Si/Al₂ ratio less than 0.17, the crystallizedsilicoaluminophosphate molecular sieve exhibits a Si/Al₂ ratio not morethan 0.08 greater than the Si/Al₂ ratio of the synthesis mixture, andthe crystallization temperature is between 150° C. and 200° C.
 29. Amethod of converting hydrocarbons into olefins comprising: (a) preparinga silicoaluminophosphate molecular sieve according to the method ofclaim 17; (b) formulating said silicoaluminophosphate molecular sieve,along with a binder and optionally a matrix material, into asilicoaluminophosphate molecular sieve catalyst composition comprisingfrom at least 10% to about 50% molecular sieve; and (c) contacting saidcatalyst composition with a hydrocarbon feed under conditions sufficientto convert said hydrocarbon feed into a product comprising predominantlyone or more olefins.
 30. The method of claim 29, wherein the hydrocarbonfeed is an oxygenate-containing feed comprising methanol, dimethylether,or a combination thereof, and wherein the one or more olefins comprisesethylene, propylene, or a combination thereof.
 31. A method of formingan olefin-based polymer product comprising: (a) preparing asilicoaluminophosphate molecular sieve according to the method of claim17; (b) formulating said silicoaluminophosphate molecular sieve, alongwith a binder and optionally a matrix material, into asilicoaluminophosphate molecular sieve catalyst composition comprisingfrom at least 10% to about 50% molecular sieve; (c) contacting saidcatalyst composition with a hydrocarbon feed under conditions sufficientto convert said hydrocarbon feed into a product comprising predominantlyone or more olefins; (d) polymerizing at least one of the one or moreolefins, optionally with one or more other comonomers and optionally inthe presence of a polymerization catalyst, under conditions sufficientto form an olefin-based (co)polymer.
 32. The method of claim 31, whereinthe hydrocarbon feed is an oxygenate-containing feed comprisingmethanol, dimethylether, or a combination thereof, wherein the one ormore olefins comprises ethylene, propylene, or a combination thereof,and wherein the olefin-based (co)polymer is an ethylene-containing(co)polymer, a propylene-containing (co)polymer, or a copolymer,mixture, or blend thereof.